CN102942970A - Combination method using semi-coke tail gas for power generation to cogenerate liquefied natural gas - Google Patents
Combination method using semi-coke tail gas for power generation to cogenerate liquefied natural gas Download PDFInfo
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- CN102942970A CN102942970A CN2012104918992A CN201210491899A CN102942970A CN 102942970 A CN102942970 A CN 102942970A CN 2012104918992 A CN2012104918992 A CN 2012104918992A CN 201210491899 A CN201210491899 A CN 201210491899A CN 102942970 A CN102942970 A CN 102942970A
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- 239000007789 gas Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000003949 liquefied natural gas Substances 0.000 title claims abstract description 20
- 238000010248 power generation Methods 0.000 title claims abstract description 15
- 239000000571 coke Substances 0.000 title abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 110
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003345 natural gas Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 8
- 239000003610 charcoal Substances 0.000 claims description 82
- 238000004140 cleaning Methods 0.000 claims description 30
- 230000009466 transformation Effects 0.000 claims description 30
- 238000006477 desulfuration reaction Methods 0.000 claims description 25
- 230000023556 desulfurization Effects 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 238000005261 decarburization Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000002737 fuel gas Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 235000009508 confectionery Nutrition 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 241000282326 Felis catus Species 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000002918 waste heat Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910017116 Fe—Mo Inorganic materials 0.000 claims description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000005611 electricity Effects 0.000 abstract description 7
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 7
- 239000011269 tar Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 4
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- -1 muriate Chemical compound 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/30—Use of alternative fuels, e.g. biofuels
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Abstract
The invention discloses a combination method using semi-coke tail gas for power generation to cogenerate liquefied natural gas. The semi-coke tail gas is pressurized by an air blower and enters a pretreatment process, and impurities of tar, naphthalene, hydrogen sulfide and the like in the semi-coke tail gas are removed; a small part of preliminary purified gas after compression enters a gas generator unit directly, and the generated power is used for liquefying natural gas in a subsequent work section; and a large part of the preliminary purified gas enters a liquefied natural gas work section and is subjected to tar and naphthalene refined removing, sulfur resistance conversion, deep purification, methanation, liquefied cryogenic separation and the like to manufacture the liquefied natural gas. According to the combination method using semi-coke tail gas for power generation to cogenerate liquefied natural gas, all chemical engineering units operate according to set rated operating conditions and need not purchase electricity externally, problems of self power generation limits and ultra-low on-grid electricity price are solved for enterprises, and the economy of semi-coke enterprises is enhanced. Simultaneously, industrial exhausted semi-coke tail gas is prepared into the clean energy of the liquefied natural gas which is shortage in China, and accordingly, efficient and clean usage of the semi-coke tail gas is achieved.
Description
Technical field
The present invention relates to environmental improvement and Energy production field, particularly a kind of combined method of utilizing blue charcoal emission power generation co-production of liquefied Sweet natural gas.
Background technology
Blue charcoal claims again semicoke, be take jurassic period non-caking coal and weakly caking coal as raw material, the solid matter of a kind of high fixed carbon content of low-temperature pyrolysis explained hereafter in the employing is gained the name because it produces blue flame when the burning.The blue charcoal tail gas of by-product and coal tar when producing blue charcoal, the about by-product 700Nm of one ton of blue charcoal of present every production
3Tail gas, calorific value 1700-2000 kilocalorie.About 1,000 ten thousand tons of the blue carbon yield in the whole nation in 2010, i.e. about 7,000,000,000 Nm of the blue charcoal tail gas of by-product
3During 12, China estimates to reach more than 5,000 ten thousand ton/years in blue charcoal market, and namely blue charcoal tail gas amount will reach 35,000,000,000 Nm
3/ year.If can not reasonably utilize these blue charcoal tail gas, certainly will cause environment to have a strong impact on, and have influence on the development of whole blue charcoal industry.
Blue charcoal tail gas also has certain difference because of its composition of difference of ature of coal, operating mode etc., and conventional blue charcoal tail gas forms such as table 1:
The typical blue charcoal tail gas of table 1 forms
| Main Components | H 2 | CH 4 | CO | CO 2 | C nH m | N 2 | O 2 | H 2O |
| v% | 20~28 | 7~10 | 14~18 | 8~12 | 1~3 | 37~43 | 0.1~0.5 | Saturated |
Also contain the impurity such as tar, benzene, naphthalene, phenol, dust, sulfide, ammonia, heavy metal in the blue charcoal tail gas in addition.
Only have in the world at present the blue charcoal of domestic product, large Doran charcoal scope of the enterprise is less, seldom has enterprise that blue charcoal tail gas is utilized, and blue charcoal tail gas generally directly is discharged in the atmosphere.At present along with country to the attention of environmental protection and the integrated development of blue charcoal industry, blue charcoal corporate boss will be used for blue this precious resources of charcoal tail gas combustion power generation, produce magnesium alloy and calcined lime etc.Because calorific value is not high, be not the most economical approach that utilizes with blue charcoal furnace exhaust gas generating.From the composition of blue charcoal tail gas as can be known, the H in the blue charcoal tail gas
2, CH
4With CO all be most valuable industrial chemicals, combined method by blue charcoal emission power generation co-production of liquefied Sweet natural gas, can solve restriction and the excessively low problem of rate for incorporation into the power network of present domestic self power generation online, simultaneously the blue charcoal tail gas of industrial discharge gas is prepared into China's clean energy natural gas liquids (LNG) in short supply, realize the high-efficiency cleaning utilization of blue charcoal tail gas, also strengthened the economy of blue charcoal enterprise.
Blue charcoal tail gas is because the uniqueness of its composition and the complicacy of impurities, the present domestic combined method that there is no take blue charcoal tail gas as raw material power generating simultaneously natural gas liquids, and blue charcoal tail gas preparing liquefied natural gas power consumption is larger, so adopt partial raw gas to generate electricity to satisfy follow-up natural gas liquids need for electricity.
Summary of the invention
The purpose of this invention is to provide a kind of combined method of utilizing blue charcoal emission power generation co-production of liquefied Sweet natural gas.Can be restriction and the excessively low problem of rate for incorporation into the power network that enterprise solves the self power generation online by the method, strengthened the economy of blue charcoal enterprise, simultaneously the blue charcoal tail gas of industrial discharge gas is prepared into China's clean energy natural gas liquids in short supply, has realized the high-efficiency cleaning utilization of blue charcoal tail gas.
To join in each methanator fresh feed gas is parallel in the methanation process of the present invention, because the first reactor is receiving unit virgin gas only, comparable the shunting reduced steam add-on and recirculation reaction tolerance, can reduce investment and the power consumption of compressor.
The minimizing of simultaneously virgin gas shunting and gas circulation amount is so that the loadings of the volume of this process reactor and catalyzer all reduces thereupon.
The technical solution used in the present invention is as follows:
The combined method of a kind of blue charcoal emission power generation co-production of liquefied Sweet natural gas (LNG) is characterized in that may further comprise the steps:
(1) air blast: blue charcoal tail gas pressure is adjusted to 0.05 ~ 0.08MPa (G);
(2) preliminary cleaning: remove the impurity that comprises tar, naphthalene, ammonia, sulphur in the blue charcoal tail gas;
(3) compression: preliminary cleaning gas is pressurized to 0.5 ~ 5.0MPa (G);
(4) generating: a part of preliminary cleaning gas after will compressing enters the fuel gas generation unit from the compressor extraction, carries out fuel gas generation, and institute's generated energy is sent to follow-up natural gas liquids operation;
(5) blue charcoal tail gas preparing liquefied natural gas:
A) purify smart detar naphthalene: another part preliminary cleaning gas after the compression enters smart detar naphthalene operation, further removes to comprise tar, naphthalene, ammonia, sulphur impurity in the blue charcoal tail gas;
B) sulfur-resisting transformation: by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio;
C) deep purifying: desulfurization and decarburization: remove with H
2S and CO
2It is main sour gas; Smart desulfurization;
D) methanation: adopt 2 ~ 4 grades of methanation reactions, obtain take methane as main high methane gas;
E) synthetic natural gas low temperature separation process liquefaction:
Enter low temperature separation process liquefaction operation after the high methane gas cooled dehydrated decarburization that step d) obtains, guarantee H before the feed liquorization
2O is less than 1ppm, CO
2Less than 50ppm; Employing is with the low temperature separation process liquefaction process of rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen; Send into liquefying plant after the methane re-heat and liquefy, obtain natural gas liquids.
In the technique scheme, step (1) is preferably used Root's blower or centrifugal blower to carry out pressure and is regulated;
In above-mentioned arbitrary technical scheme, step (3) preferably uses reciprocation compressor or radial compressor to carry out supercharging;
In above-mentioned arbitrary technical scheme, step (2) and step a) adopt the method for Temp .-changing adsorption to purify imurity-removal; Required cold blowing gas and resurgent gases are from ice chest low-pressure tail gas out in the Temp .-changing adsorption process;
In above-mentioned arbitrary technical scheme, step (4) is preheating to 100 ~ 500 ℃ with a part of preliminary cleaning gas from the compressor extraction, is that 1:2 ~ 4 pass into internal combustion turbine with air mixed according to volume ratio, carries out fuel gas generation at 600 ~ 1600 ℃.
In above-mentioned arbitrary technical scheme, the described sulfur resistant conversion process of step b) adopts the total lts technique of Partial Transformation;
In above-mentioned arbitrary technical scheme, the described conversion gas deep purifying of step c) adopts the method for wet desulphurization decarburization+smart desulfurization, guarantees to enter total sulfur≤0.1mg/Nm in the unstripped gas of methanation device
3
In above-mentioned arbitrary technical scheme, the described methanation reaction of step d) step d) comprises the steps: that the fresh feed gas that deep purifying is obtained is parallel and joins in the methanators at different levels; Adopting independently, steam supply system joins the steam recirculation that the methanation waste heat recovery produces in the reactor;
In above-mentioned arbitrary technical scheme, it number is disclosed purifying treatment method in 200810045657.4 " coke(oven)gas dry cleaning temperature swing adsorption process " that the preliminary cleaning method can adopt Chinese patent application; Also can adopt the conventional purification techniquess such as solution absorption to remove macromole impurity such as tar, naphthalene, benzene and dust in the blue charcoal tail gas, make the blue charcoal tail gas of thick purification;
In above-mentioned arbitrary technical scheme, increased organic sulfur hydrolyst in the sulfur-resisting transformation, made organosulfur transformation efficiency＞99%; The preferred EH-3 of Huashuo Science Co., Ltd type hydrolyst or the QXB-02 of Lianxin Chemical Co., Ltd., Qingdao type hydrolyst of adopting has been widely used in petrochemical industry hydrolysis organosulfur;
In above-mentioned arbitrary technical scheme, remove sour gas: can adopt MDEA method, low-temperature rectisol, NHD method or other wet method to remove the sour gas method; By this workshop section total sulfur from 500 ~ 600mg/Nm
3Be reduced to 10mg/Nm
3, CO
2Be down to 3.4 ~ 4.2% from 17 ~ 21%; The sulfide by-product sulphur cream that removes, CO
2Further concentrate utilization, (H in the gas mixture after sulfur-resisting transformation and desulfurization and decarburization processing
2-CO
2)/(CO+CO
2) mol ratio be 2.5 ~ 4.0;
In above-mentioned arbitrary technical scheme, smart desulfurization can be adopted hydrogenation+zinc oxide fine desulfurizing technology; Blue charcoal tail gas behind the desulfurization and decarburization enters hydrogenation catalyst layer (available main reactive metal is the hydrogenation catalyst of Co-Mo, Ni-Mo or Fe-Mo), then by fine desulfurization catalyst layer (available zinc oxide or special typed active carbon), purify total sulfur≤0.1mg/Nm in the rear blue charcoal tail gas
3
In above-mentioned arbitrary technical scheme, step d) methanation: adopt 2 ~ 4 grades of methanation reactions, obtain take methane as main gaseous mixture, process for synthesizing methane can adopt method commonly used in the prior art to carry out, for example: Chinese invention patent application number is 200910058611.0,201210264888.0 the method for 201210265715.0 disclosed methane (Sweet natural gas) is prepared;
The mode of CN201210264997.2 is preferably adopted in methanation: join in each methanator fresh feed gas is parallel, compare with traditional methanation process, because the fresh tolerance of reaction reduces, ratio not shunting process has reduced steam add-on and circulating flow rate, can reduce the power consumption of compressor, also reduce simultaneously the loadings of volume and the catalyzer of reactor, greatly reduced the investment of complete assembly.
The recovery of heat step: recovery of heat is to pass through interchanger preheating material gas or produce high pressure steam at each reactor outlet, and high methane gas is through the multi-stage heat exchanger recovered energy, and the rate of recovery is higher, and reaction gas recirculation is the further measure that control speed of reaction and temperature are taked.By this technique, unstripped gas is heated to temperature requiredly before taking full advantage of the heat that produces in the reaction process and will reacting, and can produce steam or superheated vapour, has saved the energy.By methanation reaction, synthetic gas is converted into by 90% above CH
4More value product with a small amount of rare gas element composition.
With steam with enter methanator after unstripped gas mixes, can control preferably temperature of reaction.This steam flow can modulation, mixes on the one hand CO+CO in the reduction unstripped gas with unstripped gas
2Concentration, the temperature of control reaction.Can reduce circulating flow rate according to practical situation on the other hand, can also be in the larger situation of unstripped gas fluctuation, control temperature of reaction, protective reaction equipment and catalyzer.Methanation catalyst can adopt prior art prepare methane used with Al
2O
3Or magnesium-aluminium spinel is carrier, and nickel is the catalyzer of active constituent, has higher high-temperature hydrothermal stability and good low temperature active.
In above-mentioned arbitrary technical scheme, the high methane gas cooling that step (e) obtains also enters low temperature separation process liquefaction operation after the molecular sieve dehydration decarburization, before the feed liquor unit, must adopt CO
2And H
2O content on line analyzer is to guarantee H
2O is less than 1ppm, CO
2Less than 50ppm;
In above-mentioned arbitrary technical scheme, in the deep purifying step, also can adopt the advanced purification process of not decarburization for this operation of device of the supplemental hydrogen source of having ready conditions, but need to replenish a large amount of hydrogen, only for there being the more enterprise of amounts of hydrogen more than needed just to be of practical significance.
In above-mentioned arbitrary technical scheme, step (e) adopts the low temperature separation process liquefaction process with rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen; Sending into liquefying plant after the methane re-heat liquefies.Natural gas liquids is sold, remaining nitrogen can beyond confession, improved the added value of blue charcoal tail gas.
In above-mentioned arbitrary technical scheme, it number is disclosed technique in 200910310615.3 or 200910310655.8 " a kind of method of utilizing coke(oven)gas to prepare natural gas liquids " that low temperature separation process can be adopted Chinese patent application.
Compare with existing blue charcoal waste gas utilization technology, the invention has the beneficial effects as follows:
(1) by the combined method with blue charcoal emission power generation co-production of liquefied Sweet natural gas provided by the present invention, the blue charcoal tail gas of small portion directly enters the fuel gas generation unit, and institute's generated energy is for follow-up workshop section natural gas liquids.The generating efficiency of fuel gas generation unit is that 35 ~ 38%(efficiency ratio steam turbine is high by 15 ~ 18%), to add smoke and waste steam boiler and can absorb 39% heat, whole efficiency of energy utilization can reach more than 70%.
(2) each chemical unit of the present invention is according to the operation of set declared working condition and need not outsourcing electric power, for enterprise has solved restriction and the excessively low problem of rate for incorporation into the power network of self power generation online, strengthened the economy of blue charcoal enterprise.Simultaneously the blue charcoal tail gas of industrial discharge gas is prepared into China's clean energy natural gas liquids in short supply, has realized the high-efficiency cleaning utilization of blue charcoal tail gas.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention
Embodiment
The present invention is described in further detail below in conjunction with embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
The blue charcoal tail gas chief component of present embodiment (vol%) is: H
2: 28.2, CH
4: 7.3, CO:16.0, CO
2: 10, C
nH
m: 0.5, N
2: 37.9, O
2: 0.1.Tolerance 50000Nm
3/ h, 40 ℃ of temperature.
(1) air blast: adopt Root's blower or centrifugal blower that blue charcoal tail gas is pressurized to 0.05 ~ 0.08MPa (G).
(2) preliminary cleaning
Adopt the dry cleaning temperature swing adsorption method, remove the macromole impurity such as tar, naphthalene, benzene and dust in the blue charcoal tail gas, make the blue charcoal tail gas of thick purification.
(3) compression: adopt reciprocation compressor or centrifugal compressor preliminary cleaning gas is pressurized to ~ 5.5MPa(G).
(4) generating: part preliminary cleaning gas enters the fuel gas generation unit from the compressor extraction.With preliminary cleaning gas be preheating to 100 ℃ ~ 500 ℃ and according to volume ratio to be 1:2 ~ 4 pass into internal combustion turbine with air mixed carries out fuel gas generation at 600 ℃ ~ 1600 ℃, institute's generated energy is sent to follow-up natural gas liquids operation.The generating efficiency of fuel gas generation unit is that 35 ~ 38%(efficiency ratio steam turbine is high by 15 ~ 18%), to add smoke and waste steam boiler and can absorb 39% heat, whole efficiency of energy utilization can reach more than 70%.About 18000 Nm of the required gas quantity that generates electricity
3/ h, generated energy is about 9000kwh.
(5) blue charcoal tail gas preparing liquefied natural gas:
A) smart detar naphthalene: another part preliminary cleaning gas enters smart detar naphthalene operation, further removes the impurity such as blue charcoal tail gas is coal-tar middle oil, naphthalene, ammonia, sulphur, to satisfy the requirement of follow-up methanation operation.
B) sulfur-resisting transformation: by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio.Corresponding process selection is suitable for the total lts technique of Partial Transformation, for solving the inadequate problem of Partial Transformation organosulfur transformation efficiency, has increased organic sulfur hydrolyst in conversion, can make organosulfur transformation efficiency＞99%.
C) deep purifying: remove sour gas.
1. desulfurization and decarburization
Blue charcoal tail gas after Partial Transformation is processed enters the MDEA decarbonization desulfurization system, and adopts Crouse+Reducing and absorption technology recovery sulphur, part CO in the conversion gas
2Be removed H in the gas
2S content is lower than 20mg/Nm
3(H in the gas mixture behind the desulfurization and decarburization
2-CO
2)/(CO+CO
2) mol ratio be 2.5 ~ 4.0, its chief component (vol%) is: H
2: 38.61, CH
4: 8.03, CO:9.89, CO
2: 1.21, C
nH
m: 0.54, N
2: 41.73, tolerance 28771Nm
3/ h.
2. deep purifying
Gas penetration depth purification system after desulfurization and decarburization is processed removes wherein remaining sulfide, muriate, ammonia and heavy metal etc., to satisfy follow-up methanation operation to the requirement of unstripped gas.Total sulfur in the unstripped gas is taken off to≤0.1mg/Nm
3, the blue charcoal tail gas after being purified.
D) methanation: the unstripped gas after deep purifying is processed enters methanation system generation methanation reaction, and byproduct steam and preheating material gas are with recovery waste heat.As follows from methanation gas chief component (percent by volume) out: H
2: 4.4, CH
4: 31.19, N
2: 64.41, tolerance 18777Nm
3/ h.
E) low temperature separation process liquefaction
Enter low temperature separation process liquefaction operation after the high methane gas cooling that step d) obtains and the dehydration decarburization, guarantee H before the feed liquorization
2O is less than 1ppm, CO
2Less than 50ppm.Employing is with the low temperature separation process liquefaction process of rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen.Sending into liquefying plant after the methane re-heat liquefies.
Liquefied natural gas (LNG)-throughput is 5673Nm in the present embodiment
3/ h, methane yield are 96%.
Nitrogen chief component (vol%) is: H
2: 6.3, CH
4: 1.78, N
2: 91.9, tolerance 13155Nm
3/ h.
Embodiment 2
The blue charcoal tail gas chief component of present embodiment (vol%) is: H
2: 28.2, CH
4: 7.3, CO:16.0, CO
2: 10, C
nH
m: 0.5, N
2: 37.9, O
2: 0.1.Tolerance 50000Nm
3/ h, 40 ℃ of temperature.
(1) air blast: adopt Root's blower or centrifugal blower that blue charcoal tail gas is pressurized to 0.05 ~ 0.08MPa (G).
(2) preliminary cleaning
Adopt the dry cleaning temperature swing adsorption method, remove the macromole impurity such as tar, naphthalene, benzene and dust in the blue charcoal tail gas, make the blue charcoal tail gas of thick purification.
(3) compression: adopt reciprocation compressor or centrifugal compressor that preliminary cleaning gas is pressurized to 0.5 ~ 2.0MPa(G).
(4) generating: part preliminary cleaning gas enters the fuel gas generation unit from the compressor extraction.With preliminary cleaning gas be preheating to 100 ℃ ~ 500 ℃ and according to volume ratio to be 1:2 ~ 4 pass into internal combustion turbine with air mixed carries out fuel gas generation at 600 ℃ ~ 1600 ℃, institute's generated energy is sent to follow-up natural gas liquids operation.The generating efficiency of fuel gas generation unit is that 35 ~ 38%(efficiency ratio steam turbine is high by 15 ~ 18%), to add smoke and waste steam boiler and can absorb 39% heat, whole efficiency of energy utilization can reach more than 70%.About 18000 Nm of the required gas quantity that generates electricity
3/ h.
(5) blue charcoal tail gas preparing liquefied natural gas:
A) smart detar naphthalene: another part preliminary cleaning gas enters smart detar naphthalene operation, further removes the impurity such as blue charcoal tail gas is coal-tar middle oil, naphthalene, ammonia, sulphur, to satisfy the requirement of follow-up methanation operation.
B) sulfur-resisting transformation: by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio.Corresponding process selection is suitable for the total lts technique of Partial Transformation, for solving the inadequate problem of Partial Transformation organosulfur transformation efficiency, has increased organic sulfur hydrolyst in conversion, can make organosulfur transformation efficiency＞99%.
C) deep purifying: remove sour gas.
1. desulfurization and decarburization
Blue charcoal tail gas after Partial Transformation is processed enters the MDEA decarbonization desulfurization system, and adopts Crouse+Reducing and absorption technology recovery sulphur, part CO in the conversion gas
2Be removed H in the gas
2S content is lower than 20mg/Nm
3(H in the gas mixture behind the desulfurization and decarburization
2-CO
2)/(CO+CO
2) mol ratio be 2.5 ~ 4.0, its chief component (vol%) is: H
2: 38.66, CH
4: 7.81, CO:8.55, CO
2: 3.83, C
nH
m: 0.53, N
2: 40.62, tolerance 29760Nm
3/ h.
2. deep purifying
Gas penetration depth purification system after desulfurization and decarburization is processed removes wherein remaining sulfide, muriate, ammonia and heavy metal etc., to satisfy follow-up methanation operation to the requirement of unstripped gas.Total sulfur in the unstripped gas is taken off to≤0.1mg/Nm
3, the blue charcoal tail gas after being purified.
D) methanation: the unstripped gas after deep purifying is processed enters methanation system generation methanation reaction, and byproduct steam and preheating material gas are with recovery waste heat.As follows from methanation gas chief component (percent by volume) out: H
2: 0.15, CH
4: 32.82, CO
2: 1.47, N
2: 65.56, tolerance 18432Nm
3/ h.
E) low temperature separation process liquefaction
The cooling of high methane gas that step d) obtains and be pressurized to 5.0MPa after go the decarburization of dewatering, then enter low temperature separation process liquefaction operation, guarantee H before the feed liquorization
2O is less than 1ppm, CO
2Less than 50ppm.Employing is with the low temperature separation process liquefaction process of rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen.Sending into liquefying plant after the methane re-heat liquefies.
Liquefied natural gas (LNG)-throughput is 5860Nm in the present embodiment
3/ h, methane yield are 96%.
Nitrogen chief component (vol%) is: H
2: 0.2, CH
4: 1.96, N
2: 97.8, tolerance 12354Nm
3/ h.
Embodiment 3
The blue charcoal tail gas chief component of present embodiment (vol%) is: H
2: 26.6, CH
4: 7.7, CO:13.2, CO
2: 11.4, C
nH
m: 0.6, N
2: 40.1, O
2: 0.4.Tolerance 50000Nm
3/ h, 40 ℃ of temperature.
(1) air blast: adopt Root's blower or centrifugal blower that blue charcoal tail gas is pressurized to 0.05 ~ 0.08MPa (G).
(2) preliminary cleaning
Adopt the dry cleaning temperature swing adsorption method, remove the macromole impurity such as tar, naphthalene, benzene and dust in the blue charcoal tail gas, make the blue charcoal tail gas of thick purification.
(3) compression: adopt reciprocation compressor or centrifugal compressor preliminary cleaning gas is pressurized to ~ 5.5MPa(G).
(4) generating: part preliminary cleaning gas enters the fuel gas generation unit from the compressor extraction.With preliminary cleaning gas be preheating to 100 ~ 500 ℃ and according to volume ratio to be 1:2 ~ 4 pass into internal combustion turbine with air mixed carries out fuel gas generation at 600 ~ 1600 ℃, institute's generated energy is sent to follow-up natural gas liquids operation.The generating efficiency of fuel gas generation unit is that 35 ~ 38%(efficiency ratio steam turbine is high by 15 ~ 18%), to add smoke and waste steam boiler and can absorb 39% heat, whole efficiency of energy utilization can reach more than 70%.About 18000 Nm of the required gas quantity that generates electricity
3/ h.
(5) blue charcoal tail gas preparing liquefied natural gas:
A) smart detar naphthalene: another part preliminary cleaning gas enters smart detar naphthalene operation, further removes the impurity such as blue charcoal tail gas is coal-tar middle oil, naphthalene, ammonia, sulphur, to satisfy the requirement of follow-up methanation operation.
B) sulfur-resisting transformation: by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio.Corresponding process selection is suitable for the total lts technique of Partial Transformation, for solving the inadequate problem of Partial Transformation organosulfur transformation efficiency, has increased organic sulfur hydrolyst in conversion, can make organosulfur transformation efficiency＞99%.
C) deep purifying: remove sour gas.
1. desulfurization and decarburization
Blue charcoal tail gas after Partial Transformation is processed enters the MDEA decarbonization desulfurization system, and adopts Crouse+Reducing and absorption technology recovery sulphur, part CO in the conversion gas
2Be removed H in the gas
2S content is lower than 20mg/Nm
3(H in the gas mixture behind the desulfurization and decarburization
2-CO
2)/(CO+CO
2) mol ratio be 2.5 ~ 4.0, its chief component (vol%) is: H
2: 41.46, CH
4: 7.52, CO:3.26, CO
2: 8.17, C
nH
m: 0.5, N
2: 39.9, tolerance 30944Nm
3/ h.
2. deep purifying
Gas penetration depth purification system after desulfurization and decarburization is processed removes wherein remaining sulfide, muriate, ammonia and heavy metal etc., to satisfy follow-up methanation operation to the requirement of unstripped gas.Total sulfur in the unstripped gas is taken off to≤0.1mg/Nm
3, the blue charcoal tail gas after being purified.
D) methanation: the unstripped gas after deep purifying is processed enters methanation system generation methanation reaction, and byproduct steam and preheating material gas are with recovery waste heat.As follows from methanation gas chief component (percent by volume) out: H
2: 0.18, CH
4: 33.05, CO
2: 0.68, N
2: 66.09, tolerance 18300Nm
3/ h.
E) low temperature separation process liquefaction
Enter low temperature separation process liquefaction operation after the high methane gas cooling that step d) obtains and the dehydration decarburization, guarantee H before the feed liquorization
2O is less than 1ppm, CO
2Less than 50ppm.Employing is with the low temperature separation process liquefaction process of rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen.Sending into liquefying plant after the methane re-heat liquefies.
Liquefied natural gas (LNG)-throughput is 5859Nm in the present embodiment
3/ h, methane yield are 96%.
Nitrogen chief component (vol%) is: H
2: 0.27, CH
4: 1.96, N
2: 97.7, tolerance 12369Nm
3/ h.
Claims (2)
1. the combined method of a blue charcoal emission power generation co-production of liquefied Sweet natural gas (LNG) is characterized in that may further comprise the steps:
(1) air blast: blue charcoal tail gas pressure is adjusted to 0.05 ~ 0.08MPa (G);
(2) preliminary cleaning: remove the impurity that comprises tar, naphthalene, ammonia, sulphur in the blue charcoal tail gas;
(3) compression: preliminary cleaning gas is pressurized to 0.5 ~ 5.0MPa (G);
(4) generating: a part of preliminary cleaning gas after will compressing enters the fuel gas generation unit from the compressor extraction, carries out fuel gas generation, and institute's generated energy is sent to follow-up natural gas liquids operation;
(5) blue charcoal tail gas preparing liquefied natural gas:
A) purify smart detar naphthalene: another part preliminary cleaning gas after the compression enters smart detar naphthalene operation, further removes to comprise tar, naphthalene, ammonia, sulphur impurity in the blue charcoal tail gas;
B) sulfur-resisting transformation: by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio;
C) deep purifying: desulfurization and decarburization: remove with H
2S and CO
2It is main sour gas; Smart desulfurization;
D) methanation: adopt 2 ~ 4 grades of methanation reactions, obtain take methane as main high methane gas;
E) synthetic natural gas low temperature separation process liquefaction:
Enter low temperature separation process liquefaction operation after the high methane gas cooled dehydrated decarburization that step d) obtains, guarantee H before the feed liquorization
2O is less than 1ppm, CO
2Less than 50ppm; Employing is with the low temperature separation process liquefaction process of rectifying, and under the refinery distillation of rectifying tower, tower reactor obtains the methane greater than 99.5% purity, and cat head obtains nitrogen; Send into liquefying plant after the methane re-heat and liquefy, obtain natural gas liquids.
2. method according to claim 1 is characterized in that: step (1) is used Root's blower or centrifugal blower to carry out pressure and is regulated.
3. method according to claim 1 and 2 is characterized in that: the method purification imurity-removal of step (2) and step a) employing Temp .-changing adsorption.
4. the described method of arbitrary claim according to claim 1-3 is characterized in that: step (3) uses reciprocation compressor or radial compressor to carry out supercharging.
5. the described method of arbitrary claim according to claim 1-4, it is characterized in that: step (4) is preheating to 100 ~ 500 ℃ with a part of preliminary cleaning gas from the compressor extraction, being 1:2 ~ 4 according to volume ratio passes into internal combustion turbine with air mixed, carries out fuel gas generation at 600 ~ 1600 ℃.
6. the described method of arbitrary claim according to claim 1-5 is characterized in that: the described sulfur resistant conversion process of step b) adopts the total lts technique of Partial Transformation.
7. the described method of arbitrary claim according to claim 1-6 is characterized in that: step c) adopts wet method to remove sour gas, makes (H in the gas mixture
2-CO
2)/(CO+CO
2) mol ratio be 2.5 ~ 4.0.
8. the described described method of arbitrary claim according to claim 1-7 is characterized in that: the blue charcoal tail gas in the step c) behind the desulfurization and decarburization enters the hydrogenation catalyst layer, then by the fine desulfurization catalyst layer, obtains total sulfur≤0.1mg/Nm
3Cleaning of off-gas.
9. method according to claim 8 is characterized in that: it is the hydrogenation catalyst of Co-Mo, Ni-Mo or Fe-Mo that described hydrogenation catalyst layer adopts reactive metal; It is fine desulfurization catalyst that the fine desulfurization catalyst layer adopts zinc oxide or special typed active carbon.
10. the described method of arbitrary claim according to claim 1-9 is characterized in that: the described methanation reaction of step d) comprises the steps: that the fresh feed gas that deep purifying is obtained is parallel and joins in the methanators at different levels; Adopting independently, steam supply system joins the steam recirculation that the methanation waste heat recovery produces in the reactor.
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Application publication date: 20130227 |